Fungicidal active compound combinations

ABSTRACT

New active compound combinations of valinamide derivatives of the formula (I)                    
     in which 
     R 1  and R 2  has the meaning given in the description, with known fungicidal active substances, and their use for combating phytopathogenic fungi are described.

This application is a division of U.S. Ser. No. 09/541,922 filed on Apr.3, 2000 (now U.S. Pat. No. 6,245,772 B1); which is a division ofapplication Ser. No. 09/110,528, filed on Jul. 6, 1998 (now U.S. Pat.No. 6,057,363); which is a division of U.S. Ser. No. 08/802,157, filedFeb. 19, 1997 (now U.S. Pat. No. 5,776,976); which is a division of U.S.Ser. No. 08/554,142, filed Nov. 6, 1995 (now U.S. Pat. No. 5,650,423);which is a division of U.S. Ser. No. 08/192,333, filed Feb. 4, 1994 (nowU.S. Pat. No. 5,491,165).

The present application relates to new active compound combinationscomposed of, on the one hand, valinamide derivatives and, on the otherhand, of other, known fungicidal active compounds, and which are highlysuitable for combating phytopathogenic fungi.

It is already known that valinamide derivatives has fungicidalproperties (cf. EP-A 472,996). The activity of this substance is good;however, it leaves something to be desired in some cases when lowapplication rates are used.

Furthermore, it is already known that a large number of azolederivatives, aromatic carboxylic acid derivatives, morpholine compoundsand other heterocycles can be employed for combating fungi (cf. K. H.Büchel “Pflanzenschutz und Schädlingsbekämpfung” [Crop Protection andPest Control] pages 87, 136, 140, 141 and 146 to 153, Georg ThiemeVerlag, Stuttgart 1977). However, the activity of the substances inquestion is not always satisfactory when low application rates are used.

It has now been found that the new active compound combinations ofvalinamide derivatives of the general formula (I)

in which

R¹ represents i-propyl or s-butyl and

R² represents chlorine, methyl, ethyl or methoxy, and

(A) dichlofluanid, of the formula

and/or

(B) tolylfluanid, of the formula

and/or

(C) tetrachloro-isophthalo-nitrile of the formula

and/or

(D) propineb, of the formula

and/or

(E) tetramethyl-thiuram-disulphide, of the formula

and/or

(F) mancozeb, of the formula

and/or

(G) dyrene, of the formula

and/or

(H) copper oxychloride

and/or

(I) captan of the formula

and/or

(K) a morpholine derivative of the formula

and/or

(L) dithianon, of the formula

and/or

(M) Phaltan, of the formula

and/or

(N) cymoxanil, of the formula

and/or

(O) propamocarb, of the formula

(CH₃)₂NCH₂—CH₂—CH₂—NHCO—OCH₂CH₃  (XIII)

or its hydrochloride

and/or

(P) fosetyl, of the formula

or the aluminium adduct thereof

and/or

(Q) metalaxyl, of the formula

and/or

(R) oxadixyl, of the formula

and/or

(S) fluazinam, of the formula

and/or

(T) methoxyacrylates, such as

methyl(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate,of the formula

and/or

(U) methoximinoacetates, such as

methyl (E)-methoximino[α-(o-tolyloxy)-o-tolyl]acetate of the formula

and/or

(V) furalaxylΛmethyl-N-(2-furoyl)-N-(2,6-xylyl)-alanit

and/or

(W) azoles of the formula

I XCl, Y=—(CH(OH)—(Triadimenol)

III X=Cl, Y=—CO-(triadimefon)

IV tebuconazole of the formula

and/or

(X) etridiazole=3-trichlormethyl-5-ethoxy-1,2,4-thiadiazole

and/or

(Y) pencycuron=1-(4-chlorbenzyl)-1-cyclopentyl(-3-phenylurea

have very good fungicidal properties.

Surprisingly, the fungicidal activity of the active compoundcombinations according to the invention is substantially greater thanthe total of the activities of the individual active compounds. Thismeans that a true synergistic effect, which could not have beenpredicted, is present, not merely a complemented activity.

It can be seen from the structural formula of the active compounds ofthe formula (I) that the compounds have two asymmetrically substitutedcarbon atoms. The product can therefore exist in the form of mixture ofvarious isomers or else in the form of a single isomer.

Preferred compounds of the formula (I) are compounds in which the aminoacid moiety is formed by ipropyloxycarbonyl-L-valine orsec-butoxycarbonyl-L-valine and the phenethylamine moiety is eitherracemic or has the S(−) configuration, but in particular the R(+)configuration.

Particularly preferred compounds of the formula (I) are the compounds inwhich R¹ represents i-propyl.

Particular mention may be made of the compounds 1-methyl-ethyl[2-methyl-1-[[[-1-(4-chlorophenyl)ethyl]-amino]carbonyl]-carbamate, ofthe formula (II)

1-Methylethyl[2-methyl-1-[[[1-(4-methylphenyl)ethyl]-amino]carbonyl]-propyl]-carbamate,of the formula (III)

1-Methylethyl[2-methyl-1-[[[-1-(4-ethylphenyl)ethyl]-amino]carbonyl]-propyl]-carbamate,of the formula (IV)

and 1-methylethyl[2-methyl-1-[[[-1-(4-methoxyphenyl)-ethyl]amino]carbonyl]-propyl]-carbamate,of the formula (V)

and their isomers, as mentioned above.

The active compounds of the formula (I) are known (cf. EP-A 472,996).

The fungicidal active compounds which are additionally present in thecombinations according to the invention are also known. The individualactive compounds are described in the following publications:

(A): K. H. Büchel “Pflanzenschutz und Schädlingsbekämpfung” [CropProtection and Pest Control], page 141, Georg Thieme Verlag, Stuttgart1977;

(B): K. H. Büchel, loc.cit., page 141 (G) p. 153

(C): K. H. Büchel, loc.cit., page 146 (H) p. 122

(D): K. H. Büchel, loc.cit., page 138 (I) p. 132, 140

(E): K. H. Büchel, loc.cit., page 136 (K) EP-A 219, 756

(F): K. H. Büchel, loc.cit., page 137 (L) p. 145

(G): K. H. Büchel, loc.cit., page 153

(H): K. H. Büchel, loc.cit., page 122

(I): K. H. Büchel, loc.cit., page 132

(K): EP-A 219,756

(L): K. H. Büchel, loc.cit., page 145

(M): K. H. Büchel, loc.cit., page 140

(O): DE 1,567,169:*

(P): FR 2,254,276:**

(Q): GB 1,500,581

(R): GB 2,058,059

(S): EP 0 31257

(T): Brighton Crop Protection Conference (1992) 5-6, 435-37

(U): Brighton Crop Protection Conference (1992) 5-6, 403-05

(V): GB 1 448 810

(W): EP-0 040 345, DE 2 324 010, DE 2 201 063

(X): U.S. Pat. No. 3,260,588

(Y): DE 2 732 257.

Besides at least one active compound of the formula (I), the activecompound combinations according to the invention comprise at least oneactive compound from amongst the compounds of groups (A) to (U). Inaddition, they can also comprise other fungicidally active componentswhich can be admixed.

The synergistic effect is particularly obvious when the active compoundsare present in the active compound combinations according to theinvention in certain ratios by weight. However, the ratios by weight ofthe active compounds in the active compound combinations can be variedwithin a relatively wide range. In general, the following amounts areemployed per part by weight of active compound of the formula (I):

1 to 50 parts by weight, preferably 2.5 to 10 parts by weight of activecompound from Group (A), 1 to 50 parts by weight, preferably 2.5 to 10parts by weight of active compound from Group (B), 1 to 50 parts byweight, preferably 1 to 10 parts by weight of active compound from Group(C), 1 to 50 parts by weight, preferably 5 to 20 parts by weight ofactive compound from Group (D), 1 to 200 parts by weight, preferably 1to 100 parts by weight of active compound from Group (E), 1 to 50 partsby weight, preferably 5 to 20 parts by weight of active compound fromGroup (F), 1 to 200 parts by weight, preferably 1 to 100 parts by weightof active compound from Group (G), 1 to 200 parts by weight, preferably1 to 50 parts by weight of active compound from Group (H), 1 to 100parts by weight, preferably 1 to 50 parts by weight of active compoundfrom Group (I), 0.5 to 10 parts by weight, preferably 1 to 5 parts byweight of active compound from Group (K), 1 to 50 parts by weight,preferably 1 to 20 parts by weight of active compound from Group (L), 1to 50 parts by weight, preferably 1 to 20 parts by weight of activecompound from Group (M), 0.5 to 20 parts by weight, preferably 1 to 10parts by weight of active compound from Group (N), 1 to 100 parts byweight, preferably 1 to 50 parts by weight of active compound from Group(O), 1 to 50 parts by weight, preferably 1 to 20 parts by weight ofactive compound from Group (P), 0.5 to 20 parts by weight, preferably 1to 10 parts by weight of active compound from Group (Q), 0.5 to 20 partsby weight, preferably 1 to 10 parts by weight of active compound fromGroup (R), 1 to 20 parts by weight, preferably 1 to 10 parts by weightof active compound from Group (S), 0.5 to 20 parts by weight, preferably1 to 10 parts by weight of active compound from Group (T) 0.5 to 20parts by weight, preferably 1 to 10 parts by weight of active compoundfrom Group (U). 0.5 to 20 parts by weight, preferably 1 to 10 parts byweight of active compound from group (V) 0.5 to 20 parts by weight,preferably 0.5 to 10 parts by weight of active compound from group (W)0.5 to 20 parts by weight, preferably 0.5 to 10 parts by weight ofactive compound from group (X), 0.5 to 20 parts by weight, preferably0.5 to 10 parts by weight of active compound from group (Y)

The active compound combinations according to the invention have verygood fungicidal properties and can be employed for combatingphytopathogenic fungi, such as, inter alia, Plasmodiophoromycetes,Oomycetes, Chyridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes andDeuteromycetes.

The active compound combinations according to the invention areparticularly suitable for protectively combating Phytophthora infestansand Alternaria spec. on tomatoes and potatoes, as well as Plasmoparaviticola on vines.

The good toleration, by plants, of the active compound combinations atthe concentrations required for combating plant diseases permits atreatment of above-ground parts of plants, of vegetative propagationstock and seed, and of the soil.

The active compound combinations according to the invention can beconverted into the customary formulations, such as solutions, emulsions,suspensions, powders, foams, pastes, granules, aerosols, very finecapsules in polymeric substances and in coating compositions for seed,as well as ULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds, or active compound combinations with extenders,that is, liquid solvents, liquefied gases under pressure, and/or solidcarriers, optionally with the use of surface-active agents, that is,emulsifying agents and/or dispersing agents and/or foam-forming agents.In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample mineral oil fractions, alcohols, such as butanol or glycol aswell as their ethers and esters, ketones, such as acetone, methyl ethylketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents, such as dimethylformamide and dimethyl sulphoxide, as well aswater. By liquefied gaseous extenders or carriers are meant liquidswhich are gaseous at ambient temperature and under atmospheric pressure,for example aerosol propellants, such as butane, propane, nitrogen andcarbon dioxide. As solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-disperse silica, alumina and silicates. Assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,maize cobs and tobacco stalks. As emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumen hydrolysis products. Asdispersing agents there are suitable: for example lignin-sulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound or combinations according to the invention can bepresent in the formulations as a mixture with other known activecompounds, such as fungicides, insecticides, acaricides and herbicides,as well as in mixtures with fertilizers or plant growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, emulsifiable concentrates, emulsions, suspensions, wettablepowders, soluble powders and granules. They are used in the customarymanner, for example by watering, spraying, atomizing, scattering,brushing on in the form of dry seed treatment, as a solution for seedtreatment a water-soluble powder for seed treatment or awater-dispersible powder for slurry treatment, or by seed coating.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a relatively wide range. They are,in general, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02% by weight, are required atthe place of action.

The good fungicidal activity of the active compound combinationsaccording to the invention can be seen from examples. While theindividual active compounds have weaknesses in . . . fungicidalactivity, the activity of the combinations exceed a simple additiveeffect.

Whenever the fungicidal activity of the active compound combinationsexceeds the total of the activities of the individually applied activecompounds, then the fungicides always show a synergistic effect.

The activity to be expected for a given combination of two activecompounds can be calculated as follows (cf. Colby, S. R., “CalculatingSynergistic and Antagonistic Responses of Herbicide Combinations”, Weeds15, pages 20-22, 1967):

If

X is the degree of effectiveness expressed as a percentage of theuntreated control when active compound A is used in a concentration of mppm,

Y is the degree of effectiveness expressed as a percentage of theuntreated control when using the active compound B in a concentration ofm ppm, and

E is the degree of effectiveness expressed as a percentage of theuntreated control, which is to be expected when using active compound Aand B in a concentration of m and n ppm,${E = {X + Y - {\frac{X - Y}{100} \cdot}}}$

If the actual fungicidal activity exceeds the calculated value, then theactivity of the combination is super-additive, i.e. a synergistic effectexists. In this case, the actually observed degree of effectiveness mustexceed the value calculated for the expected degree of effectiveness (E)using the abovementioned formula:

What is claimed is:
 1. A fungicidal composition comprising a synergisticeffective amount of a) a valinamide derivative of the formula

in which R¹ represents i-propyl or s-butyl and R² represents chlorine,methyl, ethyl or methoxy, and b) fluazinam(s) of the formula:


2. A method of combating fungi which comprises applying to such fungi orto a fungus habitat a synergistic fungicidal effective amount of acomposition according to claim 1.